Azo dyestuffs



Patented Apr. 18, 1939 UNITED STATES PATENT OFFICE AZO DYESTUFFS Max Schmid, Riehen,

Switzerland, assignor to the firm Society of Chemical Industry in Basle, Basel, Switzerland N Drawing. Original application May 14, 1937,

Serial No. 142,719. Divided and this application January 5, 1938,'Serial No. 183,534.

Switzerland November 6, 1935 8 Claims.

in which :1: is a diphenyl linking or a bridge such as O, S, CH=CH-; 'CHzCHz-, CH2, NH,

IFF 111? 25 or a heterocyclic ring such as u I o i i 30 -N-o CN- I 1 H N H (1r=hydrogen or any substituent).

and the like, and R1 is the residue of an organic acid, and condensing in known manner, after saponifying the radical of the organic acid, if this is present, with a suitable keto-compound to produce a pyrazolone capable of being coupled.

The new compounds, which correspond with 40 the general formula 1111 17TH 45 D in which a: has the meaning'ascribed to it above,

50 R1 stands for hydrogen or a radical of an organic acid and Py represents the pyrazolone radical, can be converted into new azo-dyestuffs either by coupling them with diazo-compounds or by saponifying any radical of an organic acid that may be present, then diazotizing and coupling with coupling components or by using both reactions together.

The new azo-dyestuifs are characterized by the presence of the atom grouping in which Py and a: have the meaning ascribed to them above and in which at least one azo-group is attached either to the pyrazolone radical or to the benzene nucleus which is not directly bound to the pyrazolone nucleus. They are particularly suitable for dyeing textiles consisting of or containing native or regenerated cellulose.

The

fastness of the dyeing may in many cases be improved by after-treatment with agents yielding metals, whereby metal complexes are formed on the fiber. Such metal complexes may be produced also in the dye-bath, in substance, or during the formation of dyestufi'.

As parent substances for compounds of the general formula there may be mentioned benzidine, diphenyline of. the formula IIIH:

tolidine, dianisidine, diphenetidine, thioaniline,

4 :4 -diaminodiphenyl ether, 4 4' -diaminostilbene,v 4:4-diaminodibenzyls; 4:4'- or 3:3'-diaminodiphenylmethane,

4 4 -diaminodiphenylamines, 4:4- or 4:3- or 3:4'- or 3:3-diaminobenzoylaniline, 4:4-diaminodiphenyl urea, the condensation product from 2 or 3 mol metaphenylenediamine or para-phenylenediamine and 1 mol cyanuric chloride or the condensation product from 1 mol cyanuric chloride, 1 mol aniline and 2 mol para-phenylenediamine or meta-phenylenediamine or similarly constructed condensation products in which the cyanuric ring is replaced by similar siX-membered hetero rings containing carbon and nitrogen, such as those of the pyrimidine, the quinazoline, the phthalazine, and the like, which corresponds to products in which the linkage a: can be formulated for example as Compounds of the general formula are therefore, for example, monoformylbenzidine, monoacetylbenzidine, monobenzoylbenzidine, 4- or 3-acetylamino1-(4'- or 3-amino) benzoylaminobenzene, 4-amino-1(4'- or 3'- acetylamino) benzoylaminobenzene -3- sulfonic acid, products obtained by monobenzoylation or monoacetylation from the reduced condensation products from 1 mol urea chloride or isocyanate from paraor meta-nitraniline and 1 mol 1:4- diaminobenzene-3-sulfonic acid, such as H o H sole core the ternary condensation products from 1 mol 1:4- or 1:3-diaminobenzene-3- or -4-sulfonic acid, 1 mol monoacetyl-paraor meta-phenylenediamine and 1 mol of a primary or secondary amine and 1 mol cyanuric chloride such as 11 N H l NH? N-(fi (]JN -NH. 0 0.0 In

I N N S0311 y f HN-O-OOHa and the like.

As radicals of organic acids may be mentioned inter alia the radicals of formic acid, acetic, oxalic acid, benzoic acid, propionic acid or toluene sulfonic acid.

Among the suitable keto-compounds indicated above there may be named ethyl formylacetate, ethyl acetoacetate, ethyl oxalacetate, ethyl benzoylacetate or another ethyl aroylacetate, also ethyl aroyldiacetate, for instance ethyl terephthaloyldiacetate.

From the above disclosed starting materials there are derived the products which correspond with the aforesaid general formula COOH EFO'NH O and so on, as indicated in the fifth paragraph of this specification.

Among the diazo-compounds which may be coupled with such products there must first be named the simple diazo-compounds, such as diazobenzene, diazonaphthalene, diazotoluene, diazoanisole, diazophenetole, diazotized aminoazobenzene or the like and sulfonic acids of them. Of particular interest are, however, the diazocompounds which have in orthoor peri-position to the diazo-group a hydroxyl group or a carboxyl group. Such diazo-compounds are, for example, those of ortho-aminophenols, orthoaminonaphthols and their sulfonic acids, the diazo-compounds of 1:8-aminonaphthol sulfonic acids, also of ortho-aminocarboxylic acids, for instance anthranilic acid. With the aid of such compounds dyestuffs are obtained which can be converted into valuable metal compounds on the fiber or in substance by means of agents which yield metal, for instance copper salts, chromium salts or hydroxides of these metals.

Of these dyestuifs those are of especial value which are obtained by treating with copper on with a diazotized ortho-amino-carboxylic acid of the benzene series. These new dyestufis are therefore the copper compounds of dyestu'flso! the general formula in which R2 stands for an aromatic nucleus of the benzene series which carries a COOH-group in ortho-position to the -N=N--group; when R1 is a radical of a polybasic acid, for instance dibasic acid, these dyestufis may be formulated generally as follows:-

These new dyestuffs are yellow to brown-yellow powders soluble in water to a yellow solution and producing on cotton, whether dyed as such or produced on the fiber by subsequent treatment of the non-metallized azo-dyestufi with an agent yielding copper, yellow tints which are characterized by their excellent fastness to light. They correspond to the copper compounds of the dyestufis of the general formula droxynaphthoic acid, l-acidylamino-S-hydroxynaphthalene sulfonic acid, amines such as metaphenylenediamine, B-naphthylamine, alkyl-flnaphthylamine and their sulfonic acids, azo-dyestuffs capable of coupling, and the like.

The dyestufis obtained by the invention may, as already stated, especially be used for dyeing vegetable fibers. They may also be used with a like result for dyeing regenerated cellulose, for

wherein R stands for an aromatic nucleus of the benzene series which is substituted in ortho-position to the --N:Ngroup by a COOH-group, y stands for a member of the group consisting of H, methyl, phenyl, COOH and COO-alkyl, 3: stands for a member of the group of linkages consisting of a diphenyl linkage, O-, -S,

and a heterocyclic six-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping wherein the group does not belong to the heterocyclic radical, and R1 stands for the radical of a polyvalent oranic acid.

AmOng the coupling components which may also be coupled with the diazotized compounds of the general formula in which the pyrazolone radical may be already instance, viscose or copper silk. Should the new dyestuifs contain suitable substituents they may be diazotized on the fiber and developed by further coupling components or by treatment with a diazo-cornpound. When the dyestuffs have been made with the aid of ortho-am'inophenols, ortho-aminocarboxylic acids or their esters or ethers, or when they contain the salicylic acid grouping or other lake-forming groups of atoms they are capable of conversion into metal compounds. Suitable metals coming into question besides the copper and chromium already mentioned are nickel, cobalt, iron, zinc or the like. The metal compounds may be obtained either on the fiber or in substance.

The new azo-dyestufis obtainable according to the present process correspond to the general in which R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, y stands for a member of the group! consisting of H, methyl, phenyl, COOH and COO-alkyl, :1: stands for a member of the group of linkages consisting of a diphenyl linkage, -O, -S, CH==CH-, --CH2-CH2-, CH2-, NI-I--,

and a heterocyclic siX-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 8 nitrogen atoms,

not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping l H N wherein the does not belong to the heterocyclic radical, and 2 stands for a member of a group of substituents linked to the benzene nucleus by N-atoms and consisting of a member of the group consisting of N=N'R1, R1 standing for an aromatic nucleus from the group consisting of aromatic nuclei of the benzene and naphthalene series, and

R2 standing for the radical of an organic acid, which dyestuffs are yellow to brown and black powders dissolving in water to yellow to orange, to brown to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

The following examples illustrate the invention, the parts being by weight:

Example 1 22.6 parts of finely ground monoacetyl-benzidine are stirred in 50 parts of water and some ice with 30 parts of hydrochloric acid of specific gravity 1.15. Into this mixture there is dropped slowly at 010 C. a solution of 7 parts of sodium nitrite in about 20 parts of water and when the addition of this nitrite is complete the whole is stirred for about 1 hour and then filtered.

The filtered diazo-solution is run at 0-5 C. While stirring well into an externally cooled mixture of 100 parts of stannous chloride of about 63 per cent. strength and 50 parts of hydrochloric acid of specific gravity 1.15.

The hydrazine thus formed is sparingly soluble. After stirring for about 12 hours the mixture is filtered and the solid matter washed with dilute hydrochloric acid and then with water.

is obtained. From alcohol it crystallizes in the form of bright yellow needles of melting point 227 C. Alternatively the filtered diazo-so-lution is run whilst stirring into a mixture of 632 parts of bisulfite liquor of 40 per cent. strength, 30 parts of sodium carbonate and 50 parts of caustic soda solution of 36 B. Stirring is continued during the night and the product is salted out and filtered. The filter cake is stirred into 2000 parts of water and after addition of 60 parts of acetic acid the whole is heated to boiling. There are then added gradually about 60 parts of zinc dust and boiling is continued until the mass is decolorized. After filtering hot the hydrazine sulfonic acid of the formula is salted out from. the cool filtrate.

The hydrazine sulfonic acid can be converted into the hydrochloride of the hydrazine base by treatment with hydrochloric acid.

1 In like manner products can be prepared from the parent materials indicated in the th paragraph of this specification.

Example 2 The hydrazine hydrochloride of the formula obtainable as described in paragraphs 1-3 of Example 1 is boiled together with 500 parts of Water and 100 parts of hydrochloric acid of specific gravity of 1.15 for about 2-3 hours, whereby. the hydrochloride is dissolved. If desired the solution may be treated with sulfurated hydrogen to remove tin, if necessary, filtered and cooled. The large part of the hydrochloride separates and a further quantity may be salted out from the mother liquor or the latter may be treated with alkali to recover the free base.

This base may be recrystallized from alcohol when it forms white crystals of melting point 179 C. which become brown on exposure to air and correspond with the formula The corresponding product from mono-acetylortho, ortho'-tolidine crystallizes from alcohol in white laminae of melting point 184 C. It has the formula CH3 (3H3 Example 3 The condensation may also start from the hydrazine hydrochloride and be conducted in aqueous medium. In similar manner products are obtained from the other hydrazines indicated in Example 1. Instead of ethylaceto-acetate any other fl-keto-carboxylic acid ester, for instance ethyl benzoyl acetate, terephthaloyl di-acetic ester, ethyl oxal-acetate or the sodium compounds thereof may be used.

Example 4 27.2 parts of the hydrazine hydrochloride of Example 2 are suspended in hot water. Condensation follows with 14 parts of ethylacetoacetate at about 60 C. with gradual neutralization of the acid liberated in the condensation. When the condensation is complete the whole is cooled, made alkaline to phenolphthalein by means of caustic alkali, stirred for 12 hours, heated until everything has been dissolved and finally the pyrazolone precipitated by neutralization. It corresponds with the formula t=N I C Q N- NH2 This new product is a white powder of melting point 194 C. soluble in dilute caustic soda solution and dilute mineral acid.

Example 30.? parts of 1-phenyl-(4'-phenyl-4"-acetylamino-3-methyl-5-pyrazolone of the formula obtainable as described in Example 3 are dissolved in about 500 parts of water containing parts of caustic soda solution of 36 B. and parts of calcined sodium carbonate.

The filtered solution is mixed gradually with the diazo-compound from 17.5 parts of sulfanilic acid. When coupling is complete the whole is heated and the dyestuff salted out and isolated as usual. It is an orange-yellow powder and dyes cotton yellow tints. The dyestufi corresponds with the formula By substituting for the diazotized sulfanilic acid of this example another diazo-component further direct dyeing dyestuffs may be obtained. By using non-sulfonated diazo-compounds valuable pigments are formed while when an orthohydroxyor -ortho-carboxy-diazo-compound is used dyestuffs which can be metallized are produced.

Thus, for example the dyestufi from diazotized sulfoanthranilic acid and l-phenyl-(4'-phenyli"-acetylamino) 3 methyl-S-pyrazolone produces yellow tints on viscose artificial silk or natural silk which become fast to light when aftertreated with copper. The copper compound COOH of the dyestufi dyes itself cotton yellow tints.

Further products dyeing yellow to brown-red tints are obtained by replacement of the sulfoanthranilic acid by ortho-amino-phenol-sulfonic acids of the benzene or naphthalene series, such as sulfo-amino-salioylic acid, 4-chloro-2- aminophenol-G-sulfonic acid, 4-nitro-2-aminophenol-G-sulfonic acid, l-amino 2 hydroxynaphthalene 4 sulfonic acid, 2-amino-1-hydroxynaphthalenel-:B-disulfonic acid, etc., and conversion of the new azo-dyestuffs into their copper compounds.

Similar dyestuffs can be obtained by replacing the l-phenyl (4' phenyl-4"-acetylamino) -3- methyl-5-pyrazolone by the corresponding 1- phenyl-(4'-phenyl 4" acetylamino) -5-pyrazolone-3ecarboxylic acid. Further, the 4-acetylamino group can be replaced by an amino group which is substituted by another organic acid radical. Such acid radicals may be radicals of mono-carboxylic acids, such as propionic acid, butyric acid, capric acid, benzoic acid, cinnamic acid, sulfobenzoic acid, and the like. The acetyl radical of the 4-acetylaminogroup can also be replaced by radicals of dicarboxylic acids, such as carbonic acid, oxalic acid, fumaric acid or maleic acid, phthalic acids and sulfo-phthalic acid, two or also only one carboxylic acid group being amidated. Finally, the 4-NH2-group may be substituted by such acid radicals which are not carboxylic acid radicals. As examples of these there may be cited the radicals of the paratoluene-sultonic acids or the cyanuric acid. The

introduction of such radicals into the dyestuffs of the general formula (cf. the 10th and 11th paragraph of this specification) may also take place according to known methods.

Such dyestuffs are for example the dyestufis or the copper complexes of the dyestuffs of the following formulas:-

j OQ COOH | scam-O This latter dyestuff dyes cotton green tints.

In all these dyestuffs which correspond to the general formula such dyestuifs are:

(IJHa (1H3 C=N N=C COOH cooH 3 Q1 11 n l O N=NCC H o H o H 0 H CO-N=N I II 80:11 SOBH J l H o H (3H3 311: N=c cooH C0011 N- N-C oN o-N N l 1 G1 I! I 11 1 11 1Q 3 N=NCC H 0 H 0 H 0 H O-C-N= I ll SOAH SOaH II I H a o H These dyestufis are above all valuable as metal orange brown tints, and the dyestuff of the forcompounds, and then particularly as copper commula 0 H0 so H H 9m H 0 H 9% I a I l H II I N=N-\-C-C CCN=N /N N-C- N\ (IJ=N g H N=(l3 SOaH 0H, CH9 SOaH pounds. If in these dyestuffs the diazotizing is a brown-black powder dyeing the fiber claret component R2 (cf. 10th paragraph of this specification) is an ortho-aminocarboxylic acid of the benzene series, the tints obtained therewith on cotton, artificial silk or natural silk are usually yellow. The dyeings of the copper compounds which derive from ortho-amino-carboxylic acids of the naphthalene series or from ortho-oxydiazo-compounds of the benzene or naphthalene series are orange to brown-red. Thus, for example the dyestufl of the formula yields on cotton yellow tints. The complex copper, chromium, nickel and cobalt compounds of is an orange brown powder dyeing .the tflber tints.

A furtherstrong dyeing dyestuff can be pro-- duced as follows:- 59.1 parts of the dyestufi from diazotized dehydrothiotoluidine sulfonic acid and l-phenyl-(4'-phenyl-4"-amino)-3- methyl-5-pyrazolone are treated in the usual manner with phosgene. When the reaction is complete the dyestuif formed is isolated.

It is a brown powder and dyes cellulose fibers fast orange tints.

CHa

cooH I 1 H C WN M Example 6 26.5 parts of l-phenyl-(4'-phenyl-4"-amino) 3-methyl-5-pyrazolone of the formula this dyestuff yield also yellow tints on cotton. CH3 The iron compounds yields brownish yellow tints. I N

The copper compound of the dyestuff of the l 3 C: formula CH3 CH5 0H (I3:N\ I. /N=(IJ s 01H I I N NON N I N=N-CC/ H ('i H \C-CN=NO i ll H l l I OH obtainable as described in Example 4 are dissolved in about 500 parts of water containing 10 parts of caustic soda solution of 36 B., and 15 parts of calcined sodium carbonate. To the filtered solution is added the diazo-compound from 27.7 parts of aminoazobenzene-para-sulfonic acid. For completing the coupling the whole is warmed and then the azo-dyestuff of the formula is salted out and separated as usual.

When dry it is a brown powder yielding yellow dyeings on cotton which may be converted into orange to red tints by diazotization on the fiber and developing, for instance with l-phenyl- 3-methyl-5-pyrazolone or ,c-naphthol; the tints are fast to washing.

If diazotizing components have been used which contain OH, OCH3, or 0001-! in orthoposition to the diazo-group, the products cited in Example 5 may be obtained by introducing radicals of organic acids into the amino group in 4"-position and if necessary metallizing the dyestuffs.

By application of this example numerous other monoand polyazo-dyestufis capable of development on the fiber may be produced, including dyestuffs in which the amino-group of the diphenyl-radical is diazotized in substance and coupled with such coupling components as yield dyestuffs capable of themselves being further diazotized on the fiber and developed.

Example 7 The dyestuff obtainable by coupling 26.5 parts of l-phenyl- (4-phenyl-4"-amino) -3-methyl-5- pyrazolone with the diazo-compound from 20.7 parts of 2-chloro-l-aminobenzenelasulfonic acid in a medium alkaline with sodium carbonate is dissolved in dilute caustic soda solution and the solution is mixed with 7 parts of sodium nitrite and diazotization produced by pouring the mixture into dilute cold hydrochloric acid.

The separated diazo-compound of the dyestuff acid is filtered and the filter cake is coupled in acetic acid medium with 2-amino-8-hydroxynaphthalene-6-sulfonic acid. When coupling is complete the dyestuif of the formula is separated. When dry it is a dark brown powder which dissolves in water-to a brown solution and which dyes cotton fast brown tints.

The chloraniline sulfonic acid of this example may be exchanged for any diazotizable aminocompound of the benzene or naphthalene series as Well as for such as can form complexes capable of being metallized (of. Example 5) and also by diazotlzable azo-dyestuffs.

The end component capable of being coupled can be varied and the coupling may also be produced in neutral or alkaline medium. Examples of such dyestuffs are illustrated in the following example.

Example 8 The diazo-compound of the dyestuff from diazotized ortho-chloro-sulfanilic acid and 1- phenyl- (4'-phenyl-4amino) B-methyl 5-pyrazolone obtainable as described in paragraph 1 of Example 7 is coupled in a medium alkaline with sodium carbonate with the monoazo-dyestuff obtainable by acid coupling of diazotized 2:4-dichloraniline and 1-amino-8-hydroxynaphthalene-3 6-disulfonic acid.

When dry, the isloated dyestuif of the formula OH IITH: $1

nofs S0311 O1 is a greenish black powder which dissolves in water to a green solution and dyes cotton pure strong green tints.

Further products dyeing green may be obtained if the 3-methylpyrazolone is exchanged for the corresponding 3-carboxylic acid or the benzidine radical for tolidine, dichlorobenzidine or the like. Also the yellow pyrazolone constituent and the blue-amino-naphthol constituent of the trisazo-dyestuff may be varied within wide limits. By such changes there are obtained not only green dyestuffs, but also dyestuffs which yield quite different tints. If for example in the pyrazolone constituent the ortho-chloro-sulfanilic acid is replaced by diazotized aminoazo-benzene-sulfonic acid, products are obtained which dye olive tints. Brown dyestuffs which are very fast to light are further obtained when using in the pyrazolone constituent one of the diazotizing components leading to azo-dyestuffs capable of being metallized, which are explained or suggested in Example 5, and coupling the diazotized and if necessary, already coppered or metallized pyrazolone azo-dyestuff with such azo-dyestuffs capable of coupling which have themselves been obtained by coupling 1 mol of a diazotized diazocompound, such as aniline, sulfanilic acid, anthranilic acid, ortho-aminophenol-sulfouic acid, sulfo-anthranilic acid, naphthionic acid or 1- amino-Z-hydroxynaphthalene 4 sulfonic acid with 1 mol of a compound of the group consisting of resorcin, meta-phenylenediamine, metatoluylenediamine, meta-aminophenol, naphthoresorcin, cresorcinol and the like. Those dyestufis are then particularly valuable which are also metallized in the second part of the molecule, already metallized dyestufis can then also be used as coupling components. Thus the copper, cobalt, nickel and iron compounds of the dyestufis of the formula SO H H:

N=N I HO yield on cotton brown tints.

A dyestufi dyeing blackish tints is the azo-dyestufi which is obtained by coupling in an acid medium the diazotized cupriferous dyestufi from diazotized ortho-aminophenol sulfonic acid and 1-phenyl-(4'-phenyl-4' -amino) -3-methyl-5-pyrazolone with 1-amino-8-hydroxynaphthalene- 4:6-disulfonic acid, and further coupling the disazo-dyestufi thus obtainable with diazo-benzene in an alkaline medium.

The following data serve as example of a further dyestufi of this group:-

26.5 parts of l-phenyl-(4-phenyl-4"-amin0)- 3-methyl-5-pyrazolone of Example 4 are dissolved in about 500 parts of water containing parts of caustic soda solution of 36 B. and parts of sodium carbonate. To the filtered solution is added the diazo-compound of 32 parts of dehydrothio para toluidine mono sulfonic acid. When coupling is complete the dyestuif is salted out and isolated.

This aminoazo-dyestuff is further diazotized and coupled with 37.4 parts of the copper compound of the azo-dyestuff from diazotized l-oxy- 2-aminobenzene-4-sulfonic acid and resorcinol. When coupling is complete the cupriferous disazodyestuff formed of the probable formula sulfonated azo-dyestuffs containing at least one azo-group and corresponding to the general formula in which R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, y stands for a member of the group consisting of H, methyl, phenyl, 0001-1 and COO-alkyl, 0: stands for a member of Nags the group of linkages consisting of a diphenyl linkage, -O, -S, CH=CH, CH2CH2, CH2, NH,

and a heterocyclic six-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping wherein the IIT-group does not belong to the heterocyclic radical and which is linked at least twice to the phenyl group through 'll l-groups R1 stands for the radical of a dyestuff and in s H o l H OH N=N-CC\ 1 OH N H: H Ju HOIS is isolated. which general formula further the groups When dry it is a dark brown to black powder which dissolves in water to a brown solution and dyes cotton brown fast tints. The chromium, cobalt, nickel and iron compounds of this dyestufi also yield on cotton brown tints.

In my copending application Serial No. 183,535, filed January 5, 1938 (being also a division of my application Serial No. 142,719 filed on May 14, 1937) there have been described and illustrated do not stand in ortho-position to one another, and complex metal compounds of these dyestuffs.

No claim is made herein to the complex metal compounds of such dyestufis.

What I claim is:

l. The sulfonated asymmetrical azo-dyestuffs containing at least two azo-groups of the general formula in which '1 stands for a member of the group consisting of H, methyl, phenyl, COOI-I and CO0alkyl, R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, R1 stands for an aromatic nucleus selected. from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestuffs are soluble:

in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness which can be after-treated with copper.

2. The sulfonated asymmetrical azo-dyestuffs containing at least two azo-groups of the general formula lll H0 3. The sulfonated asymmetrical azo-dyestuifs containing at least two azo-groups of the general formula in which y stands for a member of the group consisting of H, methyl, phenyl, COOH- and COOalkyl, R stands for a nucleus of the hen-- zene series substituted in ortho-position in the N=N-group by a substituent selected from the group consisting of OH and COOH groups, and R1 and R2 stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestuffs are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness which can be after-treated with copper.

4. The sulphonated asymmetrical azo-dyestuffs containing at least two azo-goups of the general formula in which R stands for a nucleus of the benzene series substituted in ortho-position to the N=N-group by a substituent selected from the group consisting of OH and COOH groups, and R1 and R2 stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestuffs are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness which can be after-treated with copper.

5. The sulfonated asymmetrical azo-dyestufis containing at least two azo-groups of the general formula in which R stands for a nucleus of the benzene series substituted in ortho-position to the N=N-group by a substituent selected from the group consisting of OH and COOI-I groups, R1 stands for a nucleus of the benzene series and R2 stands for a nucleus of the benzene series substituted in ortho-position to the --N=N-group by an OH group, which dyestuffs are soluble in water with formation of brown solutions, and dyeing the fiber similar tints which become fast when after-treated with copper.

6. The dyestuff of the formula in which the diphenyl radical does not contain a substituent, which dyestuff is soluble in water with formation of a brown solution, and dyes cotton brown tints the fastness of which can be improved by after-treating with copper.

7. The sulfonated asymmetrical azo-dyestufis of the general formula in which R and R2 stand for nuclei of the benzene series, and R1 stands for a nucleus of the naphthalene series, which dyestuffs dissolve in water with green to brown solutions and dyeing the fiber similar tints which can be after-treated substituent, which dyestufi is soluble in water with copper. with formation of a green solution, and dyes cot- 8. The azo-dyestufi of the general formula ton green tints.

,CH 5 (E 0H NH, 01 5 01 HOSWONQF I 11 11 10 H o H0|S S0111 10 in which the diphenyl radical does not contain a. MAX SCHMID. 

